JP2008107678A - Toner and method for manufacturing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner having high offset resistance and also excellent charging property while it is encapsulated toner having excellent low-temperature fixability, and to provide small particle diameter spherical toner having a sharp particle size distribution. <P>SOLUTION: The toner has encapsulated toner particles comprising toner base particles (A) containing at least a binder resin (a), a colorant and a wax, and a surface layer (B) containing a resin (b) on the surface of the toner base particles (A), wherein the binder resin (a) is a polyester-based resin, the resin (b) is the reaction product of at least a diol component and a diisocyanate component and has a carboxylic acid group, a sulfonic acid group, a salt of a carboxylic acid group or a salt of a sulfonic acid group in a side chain, and the wax is based on an ester wax and dispersed in the toner particles in a needle shape. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, a toner jet method recording method, and the like, and a manufacturing method thereof. More specifically, the present invention relates to a copying machine and printer in which a toner image is formed on an electrostatic latent image carrier and then transferred onto a transfer material to form a toner image and fixed under thermal pressure to obtain a fixed image. , Relating to toner used in fax machines.

  In recent years, energy saving has been considered as a major technical issue in electrophotographic apparatuses, and the amount of heat applied to the fixing apparatus has been significantly reduced. The need for “fixability” is increasing.

  Conventionally, in order to enable fixing at a lower temperature, the technique of making the binder resin sharper melt is known as one of the effective methods, but in this respect polyester resin has excellent characteristics. Show.

  On the other hand, as another aspect of improving the image quality, for the purpose of high resolution and high definition, the toner particle size is reduced and the particle size distribution is sharpened, while the spherical shape is improved for the purpose of improving transfer efficiency and fluidity. Toner is now being used favorably. As a method for efficiently preparing spherical toner particles having a small particle diameter, a wet method has been preferably used.

The conventional wet method is a method for preparing a toner by a so-called polymerization method such as a suspension polymerization method or an emulsion polymerization method, and has a problem that the binder resin of the toner is limited to a vinyl resin.
Therefore, as a wet method in which a sharp melt polyester resin can be used, a resin component is dissolved in an organic solvent immiscible with water, and this solution is dispersed in an aqueous phase to form oil droplets. A “dissolution suspension” method for producing spherical toner particles has been proposed (for example, Patent Document 1). According to this method, a spherical toner having a small particle diameter using polyester having excellent low-temperature fixability as a binder resin can be easily obtained.

Furthermore, capsule-type toner particles have also been proposed for the purpose of further improving the low-temperature fixability in the toner particles produced by the above-described dissolution suspension method using polyester as a binder resin.
For example, in Patent Document 2, a polyester resin, a low molecular compound having an isocyanate group, and other components are dissolved and dispersed in ethyl acetate to prepare an oil layer, and droplets are prepared in water. There has been proposed a method of preparing capsule toner particles having polyurethane or polyurea as an outermost shell by interfacial polymerization of a group-containing compound.

In Patent Documents 3 and 4, toner mother particles are prepared by a dissolution suspension method in the presence of resin fine particles of any one of vinyl resin, polyurethane resin, epoxy resin, polyester resin, or a combination thereof. A technique for preparing toner particles coated on the toner surface has been proposed.

Patent Document 5 proposes toner particles by a dissolution suspension method using urethane-modified polyester resin fine particles as a dispersant. Patent Document 6 discloses one or more film-like layers made of polyurethane resin (a). There has been proposed a core-shell type toner particle comprising a shell layer (P) and a single core layer (Q) made of a resin (b).
The capsule-type toner particles have a structure in which the heat resistance and storage stability of the shell portion is compensated for by the heat softness and poor heat storage stability of the core portion. In this case, since the shell portion is somewhat thermally hard, it is necessary to devise such as highly cross-linking or high molecular weight, so that the low-temperature fixability tends to be hindered.

  Here, according to the study by the present inventors, a compound having a bond prepared by a diol component and a diisocyanate component, that is, a compound having a urethane bond is excellent in heat resistant storage in the first place. It has been found that the heat-preserving stability can be imparted to the core without devising such as increasing the molecular weight or increasing the molecular weight, and the degree of impairing the low-temperature fixability is relatively small.

  However, when preparing capsule toner particles with polyurea as the outermost shell by the method shown in Patent Document 2, the particle size changes during the reaction time in order to prepare while reacting the surface layer, Moreover, the process may be complicated.

Patent Documents 3 and 4 also propose a method of preparing toner particles by a dissolution suspension method in the presence of polyurethane resin fine particles excellent in both heat-resistant storage stability and low-temperature fixability. However, the toner in which the polyurethane resin fine particles are arranged on the surface layer is not described in detail, and it is difficult to reach toner particles for forming a high-quality image excellent in low-temperature fixability and developability.
Further, when a polyurethane resin as described in Patent Documents 2, 3, 4, and 5 is used for the surface layer, the negative triboelectric chargeability is low, and an appropriate image may not be obtained.

  In order to solve this problem, Patent Document 6 is composed of one or more film-like shell layers (P) made of polyurethane resin (a) and one core layer (Q) made of resin (b). In the core-shell type toner particles, a proposal has been made to improve the triboelectric charging property by giving the polyurethane a sulfonic acid Na or carboxylic acid structure.

Here, the toner particles in which the polyurethane fine particles are arranged on the surface layer will be described.
According to the study by the inventors, a toner having a shell which is polyurethane, which is a reaction product of a diol component and a diisocyanate component, which are heat-resistant and has a heat-resistant storage stability and a relatively high heat resistance, is formed in the core portion. It was found that the contained wax was difficult to ooze out and sometimes had poor offset resistance.
The reason for this is not clear, but the low-polarity wax passes through the relatively high-polarity polyester, breaks through the surface layer of polyurethane, which is a reaction product of the highly polar diol component and diisocyanate component, and exudes to the toner particle surface layer. Can be difficult.

In electrophotographic fixing devices, oilless fixing is becoming the mainstream in color toners from the viewpoints of downsizing and image quality. In the case of oilless fixing, the releasability of the toner from the fixing member is expressed by the wax contained in the toner particles, so that effective wax exudation from the toner particles is an important issue in toner development. It is. In particular, when a resin having a low melt viscosity intended for low-temperature fixing is used, the toner in the molten state is likely to adhere to the fixing member, which becomes more important. If the releasability of the toner from the fixing member is poor, the melted toner adhering to the fixing member is printed on a non-image portion or the like on the paper, or the paper does not separate from the fixing member. End up.
Japanese Patent Laid-Open No. 08-248680 JP 05-297622 A JP 2004-226572 A JP 2004-271919 A Japanese Patent No. 3455523 International Publication No. 2005/073287 Pamphlet

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a toner having high offset resistance and excellent chargeability while being a capsule toner excellent in low-temperature fixability. Another object of the present invention is to provide a spherical toner having a small particle size and a sharp particle size distribution.

As a result of intensive studies to solve the above problems, the present inventors have found that at least the toner base particles (A) containing the binder resin (a), the colorant and the wax, and the toner base particles (A). A toner having capsule-type toner particles having a surface layer (B) containing a resin (b) on the surface thereof,
The binder resin (a) is a resin mainly composed of polyester,
The resin (b) is a reaction product of at least a diol component and a diisocyanate component, and has a carboxylic acid group, a sulfonic acid group, a salt of a carboxylic acid group or a salt structure of a sulfonic acid group in the side chain,
The wax has been found to solve these problems by a toner characterized in that the wax is mainly composed of an ester wax and is dispersed in a needle shape in the toner.

  According to the present invention, it is possible to provide a toner that is excellent in low-temperature fixability but has high heat resistance and offset resistance and excellent chargeability. Furthermore, it is possible to obtain a high-quality image by providing a spherical toner having a small particle size and a sharp particle size distribution.

First, features of the present invention will be described.
The first feature of the present invention is that the binder resin of the toner base particles (A) containing at least the binder resin (a), the colorant and the wax is a polyester exhibiting sharp melt properties, and the base particles (A) In the toner in which polyurethane, which is a reaction product of diisocyanate and diol, which is a surface layer that has heat-resistant storage stability and does not hinder low-temperature fixability on the surface of the toner, the wax is dispersed in a needle shape in the toner. .

  Here, a reaction product of a diol component and a diisocyanate component, that is, a compound having a urethane bond is excellent in heat-resistant storage in the first place, so that the core can be formed without extremely increasing the crosslinking density or increasing the molecular weight. It has been found that heat-resistant storage stability can be imparted to the film, and the degree to which low-temperature fixability is impaired is relatively small. However, at the same time, it has been found for the first time by the present inventors that the wax contained in the core portion is difficult to ooze out and may have poor offset resistance.

  In order to solve this problem, as a result of intensive studies by the present inventors, even in a toner in which a reaction product of a diol component and a diisocyanate component is arranged on the surface layer, an ester wax is used as the wax, and the wax is a toner. It was found that the above-mentioned problems can be solved by being dispersed in a needle shape.

First of all, since the wax is dispersed in a needle shape, the wax exists in a position closer to the surface layer of the toner in the major axis direction of the wax, and the movement path of the wax becomes short, so that the surface layer is stained. It becomes easy to take out. If the wax is dispersed in a spherical shape and trying to make the distance to the toner surface the same, a very large amount of wax is required.
There is a risk of deterioration in heat-resistant storage stability.

Second, when the wax is dispersed in a needle shape, anisotropy can be exhibited with respect to the pressure when the wax is melted and becomes liquid. That is, it is considered that when the toner is pressure-bonded in a state where the wax is in a liquid state and the toner is easily crushed, the wax is more easily crushed in the minor axis direction of the wax. As a result, it becomes easier to be crushed, excellent in low-temperature fixability, and it is considered that wax is also likely to ooze out.
By providing such a structure that the wax is likely to exude physically, the binder resin itself has a high polarity such as polyester, or a highly polar substance such as a reaction product of a diol component and a diisocyanate component. Even if it is present on the surface layer, it seems that the wax easily exudes.

  Third, the following effects can be obtained by using ester wax as the wax. As described above, a toner using polyester as a binder resin and a polyurethane with a reaction surface of a diisocyanate component and a diol component is an ideal core that has excellent low-temperature fixability and excellent storage stability.・ Although it can have a shell structure, on the other hand, it is covered completely with a strong and rigid film of polyurethane, so that it keeps the wax inside the toner, and the wax does not work substantially. The offset may become extremely bad. As a result of intensive studies by the authors in order to solve this problem, by making the wax polar using an ester wax, a polyurethane film and a moderate familiarity are expressed, and the polyurethane film is formed at a relatively low temperature. It was found that the toner surface exudes efficiently from a slight gap generated by thermal softening.

  Another feature of the present invention is that, in the toner described above, the polyurethane, which is a reaction product of the diisocyanate component and the diol component, has a carboxylic acid group, a sulfonic acid group, a salt of a carboxylic acid group or a sulfonic acid group in the side chain. It has a salt. By having this structure, it is possible to compensate for a decrease in negative chargeability due to nitrogen atoms derived from isocyanate and to obtain a highly chargeable toner. According to the study by the inventors, the enhancement of triboelectric charging is an important issue in a toner having a polyurethane, which is a reaction product of a diisocyanate component and a diol component, on the surface, particularly when the toner is used as a one-component developer. The result is that it is an indispensable structure.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments of the present invention.
In the present invention, at least a toner base particle (A) containing a binder resin (a), a colorant and a wax, and a surface layer containing a resin (b) on the surface of the toner base particle (A) ( B) a toner having capsule-type toner particles,
The binder resin (a) is a resin mainly composed of polyester,
The resin (b) is a reaction product of at least a diol component and a diisocyanate component, and has a carboxylic acid group, a sulfonic acid group, a carboxylic acid group salt or a sulfonic acid group salt in the side chain,
The wax has an ester wax as a main component and is characterized by being dispersed in a needle shape in the toner particles.
Here, the reaction product of at least the diol component and the diisocyanate component is a resin having at least a urethane bond.

<Substance with isocyanate group>
In the present invention, examples of the substance having an isocyanate group include the following.
C6-C20 aromatic isocyanate, C2-C18 aliphatic isocyanate, C4-C15 alicyclic isocyanate, C8-C15 aroma Hydrocarbon isocyanates and modified products of these isocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone group-containing modified products), and these two types It is a mixture of the above.

<Diisocyanate component used in the present invention>
The following are mentioned as said aromatic isocyanate. 1,3- and / or 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 2,4'- and / or 4, 4'-diphenylmethane diisocyanate (MDI), diaminodiphenylmethane.

  In the present invention, in addition to the diisocyanate component described above, a trifunctional or higher functional isocyanate compound may be used. Examples of the trifunctional or higher functional isocyanate compound include polyallyl polyisocyanate (PAPI), 4,4 ', 4 "-triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate, and the like.

  Examples of the aliphatic isocyanate include the following. Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl carbonate Aliphatic isocyanates such as proate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

  Examples of the alicyclic isocyanate include the following. Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1, 2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.

  Examples of the aromatic hydrocarbon isocyanate include the following. m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI). The modified polyisocyanates include those containing urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, and oxazolidone groups.

  Examples of the above modified isocyanate are as follows. Modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), isocyanate-modified products such as urethane-modified TDI, and mixtures of two or more thereof (for example, modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)) In combination with].

  Among these, preferred are 6 to 15 aromatic isocyanates, C4 to C12 aliphatic polyisocyanates, and C4 to C15 alicyclic isocyanates, and particularly preferred are TDI, MDI, HDI, Hydrogenated MDI and IPDI.

<Diol component used in the present invention>
Examples of the diol component that can be used in the present invention include the following.
Alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-
Propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, neopentylglycol, 2,2-diethyl-1,3-propanediol, etc.); The alkyl part of the alkylene ether glycol may be linear or branched. In the present invention, an alkylene glycol having a branched structure can also be preferably used.

Alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (Bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the alicyclic diol; alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) of the bisphenol ) Adducts; other polylactone diols (poly-ε-caprolactone diol, etc.), polybutadiene Njioru.

  Among these, an alkyl structure is preferable in view of solubility (affinity) in ethyl acetate, and an alkylene glycol having 2 to 12 carbon atoms is preferably used.

In the present invention, in addition to the diols described above, polyester oligomers having a terminal hydroxyl group can also be used as suitable diols.
At this time, the molecular weight of the terminal diol polyester oligomer is preferably 3000 or less, more preferably 800 or more and 2000 or less.
If the molecular weight of the oligomer is larger than this, the reactivity with the isocyanate-terminated compound is lowered, and the properties of the polyester become too strong and become soluble in ethyl acetate.

Further, the above-mentioned oligomer is preferably contained in the monomer constituting the reaction product of the diol component and the diisocyanate component in an amount of 1 mol% to 10 mol%, more preferably 3 mol% to 6 mol%.
When the terminal diol polyester oligomer is contained in an amount exceeding 10 mol%, the reaction product of the diol component and the diisocyanate component may be soluble in ethyl acetate.
If the polyester oligomer is less than 1 mol%, the reaction product of the diol component and the diisocyanate component becomes too hard to inhibit the fixing property, or the affinity with the binder resin is lowered to form a surface layer. It may be difficult.

  The polyester skeleton of the above-described polyester oligomer and the polyester skeleton of the binder resin described later are preferably the same in order to form a good core / shell. This is related to the affinity between the reaction product of the diol component and diisocyanate component on the surface layer and the core.

  Moreover, the polyester oligomer mentioned above may have an ether bond modified with ethylene oxide, propylene oxide or the like.

In the present invention, in addition to a reaction product of a diol component and a diisocyanate component, a reaction product of an amino compound and an isocyanate compound, that is, a compound having a urea bond can be used in combination.
Examples of amines that can be used in the present invention include the following. Diamines such as diaminoethane, diaminopropane, diaminobutane, diaminohexane, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 4,4 ' Diaminodicyclohexylmethane, 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate, or triamines such as triethylamine, diethylenetriamine and 1,8-diamino-4-aminomethyloctane.
In addition to the amino compound described above in the present invention, in addition to the reaction product of the diol component and the diisocyanate component, the isocyanate compound and a group having a highly reactive hydrogen such as a carboxylic acid group, a cyano group, and a thiol group. A reaction product with a compound can also be used in combination.

  In the production of the resin of the present invention, the reaction product of at least the diisocyanate component and the diol component has a structure of carboxylic acid group, sulfonic acid group, carboxylic acid group salt or sulfonic acid group salt in the side chain. It is characterized by having. The carboxylic acid group, the sulfonic acid group, the salt of the carboxylic acid group or the salt structure of the sulfonic acid group is composed of a carboxylic acid group, a sulfonic acid group, a carboxylic acid in the side chain of the monomer that forms a reaction product of the diol component and the diisocyanate component. It can be easily introduced by having a salt structure of a group or a sulfonic acid group.

Among the above monomers, a diol compound having the above-described group in the side chain can be suitably used as a versatile monomer.
Dihydroxycarboxylic acids such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolpentanoic acid, and metal salts thereof as diol compounds having a carboxylic acid group or a carboxylic acid group salt in the side chain Can be mentioned.

A monomer having a sulfonic acid group or a salt structure of a sulfonic acid group in the side chain is also effective in achieving the above object. Examples of the diol compound having a sulfonic acid group or a sulfonic acid group salt structure in the side chain include sulfoisophthalic acid, N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, and metal salts thereof. be able to.
The diol compound having a carboxylic acid group, a sulfonic acid group, a salt of a carboxylic acid group or a salt structure of a sulfonic acid group in the side chain described above is 10 mol% or more of monomers forming a reaction product of a diol component and a diisocyanate component. It is preferably contained in an amount of 50 mol% or less, more preferably 20 mol% or more and 30 mol% or less.
When the diol compound is less than 10 mol%, the dispersibility of the fine particles is deteriorated, and the granulation property may be significantly impaired. When the amount of the diol compound is more than 50 mol%, the reaction product of the diol component and the diisocyanate component may dissolve in the aqueous medium in some cases, and the function as a dispersant may not be achieved.

  In the present invention, the resin (b) that is a reaction product of the diol component and the diisocyanate component is preferably a urethane-modified polyester. The urethane-modified polyester in the present invention can be prepared by using a polyester oligomer having a terminal hydroxyl group as a diol.

<Wax used in the present invention>
In the present invention, ester wax is used as a main component as the wax. In the present invention, the ester wax only needs to have at least one ester bond in one molecule, and either natural wax or synthetic wax may be used. Here, the main component means that the ester wax occupies 50 parts by mass or more when the total amount of wax is 100 parts by mass.

Examples of synthetic ester waxes include esters of straight chain aliphatic acids and straight chain aliphatic alcohols, more specifically monoesters synthesized from long chain straight chain saturated fatty acids and long chain straight chain saturated alcohols. A wax is mentioned. Long chain straight chain saturated fatty acids have the general formula C _n H _{2n + 1}
A thing represented by COOH and n = about 5-28 is used preferably. The long-chain linear saturated alcohol is preferably represented by C _n H _{2n + 1} OH, where n = about 5 to 28.

Specific examples of the long-chain linear saturated fatty acid include capric acid, undecyl acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, pentadecylic acid, heptadecanoic acid, tetradecanoic acid, stearic acid, nonadecanoic acid, and aramonic acid. , Behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid and melicic acid.
On the other hand, specific examples of the long-chain linear saturated alcohol include amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, and myristyl alcohol. , Pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, seryl alcohol and heptadecanool.

Examples of the ester wax having two or more ester bonds per molecule include trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18. -Octadecandiol-bis-stearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate) and the like.

  Examples of natural ester waxes include candelilla wax, carnauba wax, rice wax, wax, jojoba oil, beeswax, lanolin, castor wax, montan wax, and derivatives thereof.

Other modified waxes include polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.); and dialkyl ketones (distearyl ketone).
The wax may be partially saponified.

Among the above, more preferable wax is a synthetic ester wax composed of a linear aliphatic acid and a linear aliphatic alcohol, or a natural wax mainly composed of the ester wax.
The reason for this is not clear, but it is considered that the mobility in the molten state is increased because the wax has a linear structure. In other words, it is necessary for the wax to permeate into the toner surface layer through a relatively polar substance such as polyester as a binder resin or a reaction product of diol and diisocyanate on the surface layer during fixing. In order to pass between high substances, it seems to be advantageous that the wax has a linear structure as much as possible.

  Further, in the present invention, it is more preferable that the ester is a monoester in addition to the linear structure described above. For the same reason as described above, in a bulky structure in which esters are bonded to the branched chains, it penetrates through a highly polar substance such as polyester or the surface layer of the present invention and oozes out to the surface. The authors speculate that it may be difficult.

In the present invention, it is also one of preferred modes to use a hydrocarbon wax other than the ester wax if necessary.
Examples of the above-mentioned wax include synthetic hydrocarbons such as petroleum-based natural waxes such as paraffin wax, microcrystalline wax, petrolatum, and derivatives thereof, Fischer-Tropsch wax, polyolefin wax, and derivatives thereof (polyethylene wax, polypropylene wax, and the like). Natural waxes such as ozokerite and ceresin.

In the present invention, the polarity of the ester wax achieves an affinity with the polyester and the surface layer of the present invention, and as a result, the wax is easily exuded at the time of fixing. The main component is preferably an ester wax. However, as long as it does not exceed 24.0 parts by mass with respect to the total wax when the total amount of wax is 100 parts by mass, even if the above-mentioned hydrocarbon wax is included, it is easy to exude with ester wax. It has been clarified by the inventors that it is well maintained.
This seems to be because the hydrocarbon wax has a strong affinity with the ester wax and can move with the ester wax in the polyester and the surface layer of the present invention. However, if the ratio of the hydrocarbon wax is too high, the effect of the polarity of the ester wax, which is the effect of the present invention, is not preferable.
Further, according to the study by the inventors, it has been found that a toner having particularly excellent offset resistance can be provided by mixing a hydrocarbon wax within the above range with an ester wax. The reason for this is not clear, but ester wax is partially compatible with polyester when melted, but hydrocarbon wax is extremely low in polarity, so it can exhibit a release effect efficiently without being compatible with polyester resin. I think that the.

  The mixing method of the hydrocarbon wax may be a mixture of a desired ester wax and a hydrocarbon wax at the time of toner production. Alternatively, a wax that is a mixture of an ester wax and a hydrocarbon wax like a natural wax is used. It may be used.

In the present invention, the wax content in the toner is preferably 5.0 to 20.0 mass%, more preferably 5.0 to 15.0 mass%.
When the amount is less than 5.0% by mass, the releasability of the toner cannot be maintained. When the amount is more than 20.0% by mass, the wax is likely to be exposed on the toner surface, which may cause a decrease in heat resistant storage stability.

  In the present invention, the wax preferably has a melting point of 60 ° C. or more and 90 ° C. or less in the DSC measurement of the toner. When the melting point of the wax in the DSC measurement of the toner is lower than 60 ° C., the wax is likely to be exposed on the toner surface, which may cause deterioration in heat resistant storage stability. Further, when the melting point of the wax in the DSC measurement of the toner is higher than 90 ° C., the wax does not melt properly at the time of fixing, and the low-temperature fixability and offset resistance may be inferior.

  In the present invention, the major axis of the needle-shaped wax is preferably 2.10 μm or less. If the major axis is larger than this, depending on the particle size of the toner, there is a high risk that the wax will exude to the surface layer during storage, resulting in a toner having poor storage stability.

Furthermore, in the present invention, the average value of the ratio of the major axis to the minor axis (major axis / minor axis) of the needle-shaped wax is 2.0 or more and 30.0 or less, more preferably 5.5 or more and 21.0 or less. It is preferable. That is, this is nothing but the wax being dispersed in a needle shape.
When the average value is smaller than 2.0, the wax is closer to a true sphere, and since the wax is needle-shaped, the property that the toner is liable to be crushed in the minor axis direction of the wax is hardly exhibited. In some cases, the low-temperature fixing property and the offset resistance are inferior.
If this ratio is 30.0 or more, although it depends on the particle diameter of the toner, the wax does not function as a domain, and even if it dissolves near the melting point, it immediately becomes compatible with the binder resin matrix. The function as a mold release agent is lowered, and high temperature offset is likely to occur.

In the present invention, the following production method can be suitably used as a method for simply producing the above-described capsule-type toner particles.
That is, the production method includes dissolving or dispersing at least a binder resin, a colorant and a wax in an organic medium in an aqueous medium in which fine particles containing a reaction product of a diol component and a diisocyanate component are dispersed. In this method, particles are obtained by dispersing the obtained dissolved or dispersed material, removing the solvent from the obtained dispersion and drying.

  That is, in the above system, the above-mentioned fine particles aim to be a system that also functions as a dispersant when suspending the liquid toner composition. The capsule toner of the present invention can be produced by a simpler method without requiring an aggregation step.

  When the toner particles are produced by the above production method, the wax is preferably in the form of being dispersed in advance in an organic medium before being mixed with the binder resin and the colorant. That is, a wax dispersion liquid in which a wet or dry mechanically pulverized wax is dispersed in an organic medium is prepared, and this dispersion is mixed with at least a binder resin, a colorant and an organic medium. It is a method of preparing.

According to the study by the inventors, the “needle-like” dispersion characteristic of the present invention was achieved by taking the step of finely dispersing only the wax in the organic medium in advance. The inventors consider this reason as follows.
The wax particles finely dispersed in the organic medium maintain the dispersion when the organic medium immediately after granulation is in a large state. However, as the organic medium is removed, the surrounding environment becomes rich in the binder resin. It is speculated that the following phenomenon will occur due to the change. That is, when the affinity of the wax to the binder resin is very good, the wax particles are not dispersed but uniformly dispersed while maintaining the original dispersion diameter, but the affinity for the binder resin is low. In some cases, it is considered to aggregate in the binder resin.

Here, if the affinity of the wax particles to the binder resin is too low, the wax particles aggregate immediately and form a large lump in the toner. Since the cohesive strength of the wax is weakened, it is considered that the wax particles are stacked in a form of overlapping one another. In other words, it seems to be agglomerated into elongated needles.
In fact, it has been found that the minor axis of the wax dispersion diameter observed in the toner particles in the toner of the present invention tends to depend on the wax particle diameter in the wax dispersion used.

  In the toner of the present invention, as described above, it is important to control the dispersibility of the wax in the organic medium and the appropriate affinity of the wax-dispersed particles for the binder resin. In the present invention, controlling the affinity of the wax particles by controlling the polarity and amount of the wax dispersant is also one of the preferable modes.

  The wax dispersant that can be used varies depending on the colorant, binder resin, and organic medium to be used. According to the study by the inventors, in the case where polyester is used as the binder resin and ethyl acetate is used as the organic medium. It has been found that the effects described above are easily obtained when a styrene acrylic resin having a polar group exhibiting adsorptivity to a desired colorant is used. The group that exhibits adsorptivity to the colorant varies depending on the colorant used, but an ionic group such as an anionic group such as acrylonitrile, carboxylic acid, and sulfonic acid, or a cationic group such as an amino group is preferred from the viewpoint of versatility.

Solvents that can be used as an organic medium to dissolve the binder resin and form an oil layer include hydrocarbon solvents such as ethyl acetate, xylene, and hexane, halogenated hydrocarbon solvents such as methylene chloride, chloroform, and dichloroethane, and acetic acid. Examples thereof include ester solvents such as methyl, ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane.

As an aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.
The amount of the aqueous medium used relative to 100 parts by mass of the toner composition is usually 50 to 2000 parts by mass, preferably 100 to 1000 parts by mass. If the amount is less than 50 parts by mass, the dispersion state of the toner composition is poor and a toner having a predetermined particle diameter cannot be obtained. When it exceeds 2000 parts by mass, it is not economical.

  It is also a preferable production method that an appropriate amount of an organic medium used for the oil layer is mixed in the aqueous medium used in the present invention. This seems to have the effect of enhancing the droplet stability during granulation and making the water system and the oil layer more easily suspended.

Moreover, as a dispersing agent, a well-known surfactant, a water-soluble polymer, etc. can also be used.
Main surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc., which can be arbitrarily selected in accordance with the polarity at the time of toner particle formation. Is.
For example, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphates, alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, and alkyltrimethylammonium Non-cationic surfactants such as salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, fatty acid amide derivatives, polyhydric alcohol derivatives, etc. Examples of the ionic surfactant include amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine.

  On the other hand, examples of cationic surfactants include aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, and benzas. Examples thereof include a ruconium salt, a benzethonium chloride, a pyridinium salt, and an imidazolinium salt.

A polymer dispersant may be used as the dispersant. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N- Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol, or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or esters of compounds containing vinyl alcohol and a carboxyl group For example, vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinylviridine, vinylpyrrolidone, vinylimidazole, ethyleneimine Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, polyoxyethylene alkyl, etc. Such as amine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester Celluloses such as polyoxyethylene, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and the like can be used.
When a dispersant is used, the dispersant can remain on the surface of the toner particles, but it is preferable to dissolve and remove it from the charged surface of the toner.

In the present invention, a solid dispersion stabilizer may be used to maintain a more preferable dispersion state.
In the present invention, the dispersion stabilizer is used for the following reason. That is, the organic medium in which the binder resin that is the main component of the toner is dissolved has a high viscosity, and the dispersion stabilizer surrounds the oil droplets formed by finely dispersing the organic medium with high shearing force. This is to prevent oil droplets from reaggregating and stabilizing.
As the dispersion stabilizer, inorganic dispersion stabilizers and organic dispersion stabilizers can be used. In the case of inorganic dispersion stabilizers, the toner particles are granulated in the state of adhering to the particle surface after dispersion, so that they have an affinity with the solvent. Those that can be removed by acids such as hydrochloric acid that do not contain water are preferable. For example, calcium carbonate, calcium chloride, sodium hydrocarbon, potassium hydrocarbon, sodium hydroxide, potassium hydroxide, hydroxyapatite, calcium triphosphate and the like can be used.

The dispersion method is not particularly limited, and general-purpose devices such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be used. A shearing type is preferred.
There is no restriction | limiting in particular as a stirring apparatus which has a rotary blade, If it is a general thing as an emulsifier and a disperser, it can be used.
For example, Ultra Tarrax (manufactured by IKA), Polytron (manufactured by Kinematica), TK Auto Homo Mixer (manufactured by Special Machine Industries Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK Homomic Line Flow (Made by Special Machine Industries Co., Ltd.), colloid mill (made by Shinko Pantech Co., Ltd.), slasher, trigonal wet pulverizer (made by Mitsui Miike Chemical Co., Ltd.), Cavitron (made by Eurotech), fine flow mill Examples include continuous type emulsifiers (made by Taiheiyo Kiko Co., Ltd.), batch types such as Claremix (made by M Technique Co., Ltd.), fill mix (made by Tokushu Kika Kogyo Co., Ltd.), and continuous two-way emulsifiers. .

When a high-speed shearing disperser is used, the rotation speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 3000 to 20000 rpm.
In the case of a batch system, the dispersion time is usually 0.1 to 5 minutes. The temperature during dispersion is usually 10 to 150 ° C. (under pressure), preferably 10 to 100 ° C.

In order to remove the organic medium from the emulsified dispersion obtained in this manner, a method of gradually elevating the temperature of the entire system and completely evaporating and removing the organic medium in the droplets can be employed.
Alternatively, it is also possible to spray the emulsified dispersion in a dry atmosphere, completely remove the water-insoluble organic medium in the droplets to form toner fine particles, and evaporate and remove the aqueous dispersant together.
In that case, the dry atmosphere in which the emulsified dispersion is sprayed is generally a gas heated with air, nitrogen, carbon dioxide gas, combustion gas, or the like, particularly various air streams heated to a temperature higher than the boiling point of the highest boiling solvent used. Used.

Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.
When the particle size distribution at the time of emulsification dispersion is wide, and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but more preferably, the dispersant is removed simultaneously with the classification operation.
The resulting dried toner powder is mixed with different kinds of particles such as release agent fine particles, charge control agent fine particles, fluidizing agent fine particles, and colorant fine particles, and mechanical impact force is applied to the mixed powder. In this way, it is possible to fix and coalesce on the surface, and to prevent the dissociation of foreign particles from the surface of the resulting composite particle.

  In the above manufacturing method, it is possible to further provide a heating step after removing the organic medium. By providing the heating step, the toner surface can be smoothed and the degree of spheroidization can be adjusted.

  Preparation of resin fine particles mainly composed of the resin used in the present invention is not particularly limited, and the emulsion polymerization method or resin is dissolved in a solvent or melted to be liquefied, and this is liquefied in an aqueous medium. It can be prepared by granulating it by suspending it. At this time, known surfactants, dispersants, and the like can be used, and the resin constituting the fine particles can be made self-emulsifying.

  Solvents that can be used when preparing the fine particles by dissolving the resin in a solvent are not particularly limited, but hydrocarbon solvents such as ethyl acetate, xylene, and hexane, halogens such as methylene chloride, chloroform, and dichloroethane. Hydrocarbon solvents, ester solvents such as methyl acetate, ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane, methanol, Examples include alcohol solvents such as ethanol and butanol.

  Further, in the present invention, it is one of the preferred modes to use resin fine particles containing a reaction product of a diol component and a diisocyanate component as a dispersant. This production method produces a prepolymer having an isocyanate group, A method in which this is rapidly dispersed in water, followed by addition of a compound having an amino group capable of reacting with an isocyanate group to extend the chain or to be crosslinked can be preferably used.

  That is, in the present invention, a prepolymer having an isocyanate group and other necessary components as necessary are dissolved or dispersed in a solvent having high solubility in water such as acetone or alcohol among the above solvents, and this is dissolved in water. A method for preparing a reaction product of a diol component having a desired physical property and a diisocyanate component by rapidly dispersing the prepolymer system having the isocyanate group and subsequently introducing an amino group-containing compound. It can be used suitably.

As the resin fine particles, those having a number average particle diameter of 10 to 120 nm are preferably used, and more preferably 20 to 100 nm are preferable for forming a capsule structure which is a feature of the toner of the present invention. That is, when the number average particle diameter is smaller than 10 nm, as in the case where the coating amount of the resin fine particles is small, when the toner of the present invention is manufactured in an aqueous system, the granulation stability is lowered. Therefore, it becomes difficult to form a capsule structure, and the heat resistant storage stability tends to deteriorate. On the other hand, when the particle size is larger than 150 nm, as in the case where the coating amount of the resin fine particles is large, when the toner of the present invention is produced in an aqueous system, the dispersibility in the aqueous phase is lowered, Unification of particles or irregularly shaped particles.

  In the present invention, the reaction product of diisocyanate and diol preferably has a 1/2 melting temperature value Tm1 / 2 by a flow tester of 85 ° C. or higher and 150 ° C. or lower. When the temperature is lower than 85 ° C., the contamination of the member may be remarkable particularly when printing is performed at a high speed for a long time. On the other hand, if the temperature is higher than 150 ° C., not only low temperature offset is likely to occur, but also the glossiness is remarkably lowered, which causes a reduction in image quality.

In the capsule toner of the present invention, it is more preferable that the toner base particles are completely covered with the surface layer.
The inventors consider that the following is important in order to develop good fixing characteristics after completely covering the toner base particles with the surface layer.
In the present invention, when resin fine particles are used for forming the toner surface layer, the resin fine particles are preferably contained in an amount of 2.0 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the toner particles.
When the amount of the resin fine particles is less than 2.0 parts by mass, although depending on the particle size of the resin fine particles and the particle size of the toner, the surface layer coating may not be complete and the heat resistant storage stability may be poor.
If the amount of the resin fine particles is more than 15.0 parts by mass, the heat of the fixing member is difficult to be transferred to the inside of the toner, and the low-temperature fixing property is impaired. It may be inferior in offset resistance.

  In the present invention, the toner preferably has a weight average particle diameter of 2.0 or more and 10.0 μm or less. If the toner particle diameter is smaller than this, the toner will be charged up, especially after a long period of use, causing problems such as a decrease in density. When the weight average particle diameter of the toner is larger than 10.0 μm, the line image or the like is likely to be scattered or fall out, resulting in poor fine line reproducibility.

In the present invention, the sphericity SF-1 of the toner is preferably in the range of 100 to 140, more preferably 100 to 130.
When the SF-1 value is larger than 140, the transfer characteristics tend to be lowered, and the image may be deteriorated. That is, when the SF-1 value is 100, a shape close to a true sphere is shown, and therefore a toner shape closer to 100 is preferable.

  Furthermore, in the present invention, the molecular weight measured by gel permeation chromatography (GPC) of the binder resin in tetrahydrofuran (THF) is preferably 8000 or less, more preferably less than 5500. One. Furthermore, it is one of the preferable embodiments that the ratio of the molecular weight of 100,000 or more is 5.0 area% or less, more preferably 1.0% area or less.

  If the peak molecular weight is 8000 or more, or the ratio of the molecular weight is 100,000 or more is 5.0 area% or more, the fixability may be remarkably impaired depending on the type and amount of the surface layer resin. In the present invention, the ratio of the binder resin having a molecular weight of 1000 or less is preferably 10.0 area% or less, more preferably less than 7.0 area%. When the ratio of the molecular weight of 1000 or less is more than 10.0 area%, the low molecular weight component that is relatively thermally unstable may contaminate the member.

In the present invention, in particular, the following preparation method can be suitably used in order to make the ratio of the molecular weight of 1000 or less to 10.0 area% or less. In order to reduce the ratio of the molecular weight of 1000 or less, the present inventors effectively reduce the ratio of the molecular weight of 1000 or less by dissolving the binder resin in a solvent and leaving the solution in contact with water. I found that I can do it. That is, it is considered that the low molecular weight component having a molecular weight of 1000 or less is eluted in water by such an operation and can be effectively removed from the binder resin solution.

  From the above, in the present invention, the above-described dissolution suspension method is used as a toner production method, and before the solution in which the binder resin, the colorant, and the wax are dissolved or dispersed is suspended in the aqueous medium. The low molecular weight component can be efficiently removed by using a method of leaving it in contact with an aqueous medium.

  Further, in the present invention, there is a possibility that the molecular chain may be cut off by melting and kneading the binder resin or applying excessive stress in the solution, and the low molecular weight component may be increased. It is not preferable to provide it.

  The toner of the present invention is characterized in that a polyester resin is a main component as a binder resin in order to achieve a toner that can be fixed at a low temperature. Here, the main component means that the polyester occupies 50 parts by mass or more when the binder resin is 100 parts by mass.

Examples of the polyester monomer that can be used as the binder resin of the toner of the present invention include the following.
The alcohol component is preferably an aliphatic alcohol having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms. Examples of the aliphatic alcohol having 2 to 8 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-butenediol, 1,7-heptanediol, 1,8- Examples thereof include linear diols such as octanediol, hydrogenated bisphenol A, bisphenol derivatives represented by the following (formula 1), and diols represented by the following (formula 2).

Moreover, it is preferable that the polyester skeleton of the above-described polyester oligomer and the polyester skeleton of the binder resin described later are the same in consideration of the affinity between the reaction product of the diol component and the diisocyanate component on the surface layer and the core.
That is, in the present invention, considering the insolubility of the reaction product of the diol component and diisocyanate component on the surface layer in ethyl acetate, the non-aromatic, that is, alkyl type is preferable to the aromatic skeleton. It is also preferable to use a polyester using an alkyl diol.

Further, from the viewpoint of durability, the content thereof is 30 to 100 mol%, preferably 50 to 100 mol%, in the alcohol component.
As carboxylic acid components, aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, fumaric acid, maleic acid, adipic acid, succinic acid, dodecenyl succinic acid, octenyl succinic acid Aliphatic polycarboxylic acids such as succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, anhydrides of these acids and alkyls of these acids (1 carbon atom) -8) Esters and the like.

  From the viewpoint of chargeability, the carboxylic acid component preferably contains an aromatic polyvalent carboxylic acid compound, and the content thereof is preferably 30 to 100 mol%, and 50 to 100 mol% in the carboxylic acid component. Is more preferable. The raw material monomer may contain a trivalent or higher polyhydric alcohol and / or a trivalent or higher polyvalent carboxylic acid compound.

In the toner of the present invention, in addition to the polyester resin, a styrene-acrylic resin, a mixed resin of polyester and styrene-acryl, an epoxy resin, or the like may be contained.
In the present invention, when the molecular weight of the toner is adjusted, a binder resin having two or more kinds of molecular weights may be mixed and used.

As the colorant used in the color toner in the present invention, the following are used.
As a colorant suitable for the yellow color, a pigment or a dye can be used. Specifically, the following are mentioned as a pigment. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 17, 23, 62, 65, 73, 74, 81, 83, 93, 94, 95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 138, 139, 147, 151, 154, 155, 167, 168, 173, 174, 176, 180, 181, 183, 191, C.I. I. Bat yellow 1,3,20. Examples of the dye include the following. C. I. Solvent yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162. These are used alone or in combination of two or more.

As a colorant suitable for magenta, a pigment or a dye can be used. Specific examples include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48; 2, 48; 3, 48; 4, 49, 50, 51, 52, 53, 54, 55, 57, 57; 1, 58, 60, 63, 64, 68, 81, 81; 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254; C.I. I. Pigment violet 19; C.I. I. Vat Red 1, 2, 10, 13, 15, 23, 29, 35. Examples of the magenta dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122, etc. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disperse Violet 1; I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as basic violet 1,3,7,10,14,15,21,25,26,27,28. These are used alone or in combination of two or more.

  As a colorant suitable for cyan, a pigment or a dye can be used. Specific examples include the following. C. I. CI pigment blue 1, 7, 15, 15; 1, 15; 2, 15; 3, 15; 4, 16, 17, 60, 62, 66; I. Bat Blue 6, C.I. I. Acid Blue 45. Examples of the dye include the following. C. I. Solvent Blue 25, 36, 60, 70, 93, 95. These are used alone or in combination of two or more.

  The following are mentioned as a black pigment. Carbon black such as furnace black, channel black, acetylene black, thermal black, lamp black. Magnetic powders such as magnetite and ferrite are also used.

  In the present invention, it is not preferable to use a dye or pigment having extremely high solubility in water as the colorant. When the above-mentioned dyes / pigments are used, they may dissolve in water during the production process, and granulation may be disturbed or desired coloration may not be obtained.

In the present invention, a charge control agent can be used as necessary. The charge control agent may be contained in a toner core portion containing at least a binder resin and a pigment, or may be contained in a surface layer that is a reaction product of a diol component and a diisocyanate component.
Examples of the charge control agent include the following. Nigrosine dyes, triphenylmethane dyes, metal-containing azo complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, simple substances of phosphorus Alternatively, a compound, a simple substance or compound of tungsten, a fluorine-based activator, a salicylic acid metal salt, and a salicylic acid derivative metal salt.
Specific examples include the following. Bontron N-03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E-84 of salicylic acid metal complex, Phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt Copy charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX
VP434 (above, manufactured by Hoechst), LRA-901, LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigment, other sulfonic acid groups, carboxyl groups and quaternary ammonium salts A polymer compound having a functional group such as

  In the classification operation, fine particles can be removed in the liquid by a cyclone, a decanter, a centrifugal separator or the like. Of course, the classification operation may be performed after obtaining the powder after drying, but it is preferable in the liquid to perform the classification operation. The obtained unnecessary fine particles or coarse particles can be returned to the dissolving step and used for forming particles. At that time, fine particles or coarse particles may be wet.

As the external additive for assisting the fluidity, developability and chargeability of the toner particles obtained in the present invention, inorganic fine particles can be preferably used.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, particularly 5 nm to 5 μm.
It is preferably 00 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.
The use ratio of the inorganic fine particles is preferably 0.01 to 5.0% by mass of the toner particles, and particularly preferably 0.01 to 2.0% by mass.
These inorganic fine particles may be used alone or in combination of plural kinds.

  Specific examples of the inorganic fine particles include the following. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, Examples include Bengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. In addition to this, polymer fine particles, polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, and particles of polymers such as silicone, benzoguanamine, and nylon are exemplified.

The fluidizing agent typified by the above-mentioned inorganic fine particles can be surface-treated to increase the hydrophobicity and prevent deterioration of the flow characteristics and charging characteristics even under high humidity.
For example, a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, modified silicone oil, and the like are preferable surface treatment agents. .

  Examples of the cleaning performance improver for removing the developer using the toner of the present invention after transfer remaining on the photoreceptor or primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, such as polymethyl Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 mass of toner with respect to 100 mass parts of the carrier. Part is preferred.
As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, and magnetic resin carrier having an average particle diameter of 20 to 200 μm can be used.

<Measurement of melting point of wax and content of wax>
The method for measuring the melting point of the wax and the wax content in the toner in the present invention is DSC.
The measurement was performed under the following conditions using Q1000 (manufactured by TA Instruments) and calculated.
<< Measurement conditions >>
・ Modulation mode ・ Temperature increase rate: 0.5 ℃ / min
Modulation temperature amplitude: ± 1.0 ° C / min
・ Measurement start temperature: 25 ℃
・ Measurement end temperature: 130 ℃

<< Calculation method of wax melting point >>
The wax alone or the toner was measured under the above conditions, and the peak value of the endothermic peak in the DSC measurement of the toner was taken as the melting point of the wax in the present invention. When two or more peaks exist, the peak with the higher endotherm was taken as the melting point. In addition, the maximum endothermic peak when measured with a single wax is simply expressed as “melting point” in the present specification.

<< Calculation method of wax content in toner >>
DSC measurement of a single wax was performed under the above conditions, and Rev Cp (J / g / ° C.) on the vertical axis
Is displayed, and the integral value of the endothermic peak of the wax is calculated in an arbitrary temperature range. This is Cp_wax. Next, DSC measurement of the toner is performed under the same conditions, and the integrated value of the endothermic peak of the wax in the toner is calculated under the same conditions and temperature range. This is Cp_toner.
From the measured value, the wax content in the toner was calculated by the following formula.

また本発明においては、ワックスを２種以上用いている場合には、それぞれのワックスについて別々に含有量を算出し、その和をワックスの含有量とした。

Moreover, in this invention, when using 2 or more types of wax, content was calculated separately about each wax, and the sum was made into content of wax.

<Measurement of Tg>
In the present invention, the Tg measurement of the toner is also DSC measurement under the same conditions as the measurement of the melting point and the wax content of the wax, and the DSC curve is obtained by taking “Reversing Heat Flow” on the vertical axis. The onset value shown in FIG. 2 was defined as Tg of the present invention.

<Wax dispersion diameter / shape>
In the present invention, the average wax dispersion particle size and dispersion shape were as follows.
An ultrathin section of the test toner was prepared, and the cross section was dyed with ruthenium to stain the wax in the toner. Subsequently, the transmission image of the stained sample was observed at 14,000 times with a transmission microscope (TEM) H-7500 manufactured by Hitachi, Ltd., and a digital observation image was obtained. Subsequently, the shape of the wax part in the toner was measured from the digital image with the image processing software Win-Roof as follows.
<< Longer diameter of needle-shaped wax >>
Attention was paid to one wax particle dispersed in one toner on the image, and the longest part was defined as the long diameter.
<< Short diameter of needle-shaped wax >>
A straight line was drawn at right angles to the midpoint of the major axis of the wax obtained as described above, and the minor point of the wax was defined between the two points where the straight line was in contact with the outer shape of the wax particles.
When there are many wax particles in one toner, the same measurement is performed for all the wax particles in one toner, and the average values of the major axis and the minor axis in one toner are calculated. The dispersion diameter of the wax in one toner was used.
The major axis and minor axis were measured for a total of 50 toners and averaged to calculate the major axis and minor axis of the wax dispersed particles in the toner of the present invention.
<< Ratio of major axis to minor axis of needle-shaped wax >>
From the major axis and minor axis calculated as described above, the ratio between them was calculated using the following formula.
Ratio of major axis to minor axis = major axis / minor axis

<Measurement of molecular weight>
In the present invention, the molecular weight distribution of the chromatogram by GPC (gel permeation chromatography) using the THF (THF) soluble portion of the toner (binder resin) as a solvent is measured under the following conditions.
The measurement sample is prepared as follows.
Mixing the sample and THF at a concentration of about 0.5-5 mg / ml (eg about 5 mg / ml);
After leaving it to stand at room temperature for several hours (for example, 5 to 6 hours), shake it well, mix the sample with THF well (until the sample is completely united), and further at room temperature for 12 hours (for example, 24 hours) Leave still. At this time, the time from the start of mixing the sample and THF to the end of standing is set to 24 hours or longer.
Then, GPC was passed through a sample processing filter (pore size 0.45-0.5 μm, for example, Mysori Disc H-25-2 manufactured by Tosoh Corp., Excro Disc 25CR manufactured by Gelman Science Japan Co., Ltd., etc.). This sample.
The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

The column was stabilized in a 40 ° C. heat chamber, and THF as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. Measurement is performed by injecting 50 to 200 μl of a THF sample solution.
In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3. It is appropriate to use 9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
As a column, in order to accurately measure a molecular weight region of 10 ³ to 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. In the present invention, measurement is performed under the following conditions. Is done.
[GPC measurement conditions]
Equipment LC-GPC 150C (Waters)
Column KF801, 802, 803, 804, 805, 806, 807 (manufactured by Shodex) Column temperature 40 ° C
solv. THF (tetrahydrofuran)
In general, in the measurement of the GPC chromatogram, the high molecular weight side starts measurement from the starting point of the rise of the chromatogram from the baseline, and the low molecular weight side measures up to a molecular weight of about 400.

<Method for measuring weight average particle diameter of toner>
A Coulter counter Multisizer II (manufactured by Coulter, Inc.) is used as a measuring device. As the electrolyte, first grade sodium chloride is used to prepare an approximately 1% NaCl aqueous solution. For example, ISTON R-II (manufactured by Coulter Scientific Japan) can be used.
As a measuring method, 0.1 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 ml of the electrolytic aqueous solution, and 5 mg of a measurement sample is further added. The electrolyte in which the sample is suspended is subjected to a dispersion treatment for about 3 minutes with an ultrasonic disperser, and the volume and number of toner particles having a particle diameter of 2.00 to 40.30 μm are measured using the 100 μm aperture as the aperture. Measurement is performed for each channel, and the volume average particle diameter Dv and the number average particle diameter Dn1 are calculated from the volume distribution and number distribution of the toner, respectively. Then, a weight-based weight average particle diameter obtained from the volume distribution is obtained. As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00-40.30 μm are used.

<Measurement method of particle size of resin particles, wax particles in wax dispersion>
Using a Microtrac particle size distribution analyzer HRA (X-100) (Nikkiso Co., Ltd.), measurement is performed in a range of 0.001 μm to 10 μm, and the number average particle diameter μm is determined as the resin fine particles and wax particles according to the present invention. The diameter. As dilution solvents, water was selected for the resin fine particles, and ethyl acetate was selected for the wax particles.

<Measurement method of circularity>
In the present invention, SF-1 indicating shape factor is FE-SEM (S-800) manufactured by Hitachi, Ltd., and 100 toner images of 2 μm or larger magnified 1000 times are sampled randomly. Through the interface, the image is introduced into the image analysis apparatus (Luxex III) manufactured by Nicole and analyzed, and the value obtained from the following equation is defined as the shape factor SF-1.

<Method for evaluating heat-resistant storage stability>
About 10 g of toner was put in a 100 ml polycup and allowed to stand at 50 ° C. for 3 days, and then visually evaluated.
(Evaluation criteria)
A: Aggregates are not seen.
B: Although aggregates are seen, they break apart easily.
C: Aggregates can be grasped and do not collapse easily.

この定着開始温度を以下のような評価基準で評価した。
Ａ：１２０℃以下
Ｂ：１２０℃＜定着開始温度≦１４０℃
Ｃ：１４０℃＜定着開始温度≦１６０℃
Ｄ：定着開始温度＞１６０℃
なお、本発明においては上記Ｂランクまでを良好な低温定着性と判断した。 <Fixing start temperature (low temperature fixability)>
In the color laser copier CLC5000 (manufactured by Canon Inc.), the development contrast is adjusted so that the amount of toner on the paper is 1.2 mg / cm ² in a single color mode at room temperature and humidity (23 ° C./60%). A solid unfixed image having a margin of 5 mm, a width of 100 mm, and a length of 280 mm was prepared. As the paper, cardboard A4 paper (“Prober Bond paper”: 105 g / m ² , manufactured by Fox River) was used.
The fixing device of CLC5000 (manufactured by Canon Inc.) was remodeled, and the fixing unit was set at a fixing temperature manually, and it was 80 ° C. to 200 ° C. in a normal temperature and humidity environment (23 ° C./60%). The fixing test was performed by increasing the temperature by 10 ° C in order.
The image area of the obtained fixed image was rubbed back and forth 5 times while applying a load of 4.9 kPa from a soft thin paper (for example, trade name “Dasper”, manufactured by Ozu Sangyo Co., Ltd.). The subsequent image density was measured, and the reduction rate ΔD (%) of the image density was calculated by the following equation (8). The temperature at which ΔD (%) was less than 10% was determined as the fixing start temperature.
The image density was measured with an X-Rite color reflection densitometer (Color reflection densitometer X-Rite 404A).

This fixing start temperature was evaluated according to the following evaluation criteria.
A: 120 ° C. or less B: 120 ° C. <fixing start temperature ≦ 140 ° C.
C: 140 ° C. <fixing start temperature ≦ 160 ° C.
D: Fixing start temperature> 160 ° C.
In the present invention, it was determined that the above rank B was good low-temperature fixability.

<Evaluation of offset resistance>
A fixing test was conducted in accordance with the measurement of the fixing start temperature, and the temperature at which offset (peeling) and wrapping occurred on the fixed image was visually evaluated.
The offset resistance was evaluated according to the following evaluation criteria.
AA: Neither high temperature offset nor wrapping occurs A: A very slight high temperature offset is observed at 190 ° C or higher B +: A high temperature offset is observed at 190 ° C or higher B: Offset is slight at 180 ° C or higher and lower than 190 ° C B: observed at 180 ° C. or more and less than 190 ° C. C: offset or winding is observed at less than 180 ° C. In the present invention, the above-mentioned B-rank is excellent in offset resistance. It was judged.

<Evaluation of electrification>
The method for measuring the triboelectric charge amount of the toner in the present invention will be described below. First, a predetermined carrier and toner particles are placed in a plastic bottle with a lid, and shaken for 1 minute at a speed of 4 reciprocations per second with a shaker (YS-LD, manufactured by Yayoi Co., Ltd.). The developer consisting of is charged. Next, the triboelectric charge amount is measured in the apparatus for measuring the triboelectric charge amount shown in FIG. In FIG. 3, about 0.5 to 1.5 g of the developer described above is put in a metal measuring container 2 having a 500 mesh screen 3 at the bottom, and a metal lid 4 is formed. The mass of the entire measurement container 2 at this time is weighed and is defined as W1 (g). Next, in the suction machine 1 (at least the part in contact with the measurement container 2) is sucked from the suction port 7 and the air volume control valve 6 is adjusted so that the pressure of the vacuum gauge 5 is 250 mmAq. In this state, the toner particles are sucked and removed by suction for 2 minutes. The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor, and the capacity is C (mF). Further, the mass of the entire measurement container after suction is weighed and is set to W2 (g). The triboelectric charge amount (mC / kg) of this sample is calculated as follows.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

[Preparation of resin fine particle dispersion 1]
100 parts by mass (0.05 mol) of a polyester diol having a number average molecular weight of about 2000 obtained from a 40:50:10 mol mixture of propylene glycol, ethylene glycol and butanediol and an equimolar mixture of terephthalic acid and isophthalic acid

・ 16 parts by mass of propylene glycol (0.24 mol)
・ 94 parts by mass (0.7 mol) of dimethylolpropanoic acid
・ Sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate

8 parts by mass (0.03 mol)
・ Tolylene diisocyanate 30 parts by mass (0.2 mol)

The raw material was dissolved in 60 parts by mass of acetone and reacted at 67 ° C. for 1 hour.
Next, 271 parts by mass (1.2 mol) of isophorone diisocyanate was added, and the mixture was further reacted at 67 ° C. for 30 minutes and cooled.
After adding 100 parts by mass of acetone to the reaction product, 80 parts by mass (0.8 mol) of triethylamine was added and stirred.
The acetone solution was added dropwise to 1500 parts by mass of ion-exchanged water while stirring at 500 rpm to prepare a fine particle dispersion.
Next, an aqueous solution in which 50 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% ammonia water was added and reacted at 50 ° C. for 8 hours to carry out an elongation reaction to obtain a resin fine particle dispersion 1.

<Example 1>
<Preparation of wax dispersion>
Stearate stearate (melting point 60 ° C.) 16 parts by mass Nitrile group-containing styrene acrylic resin (65 parts by mass of styrene, 35 parts by mass of n-butyl acrylate, 10 parts by mass of acrylonitrile, peak molecular weight 8500)
8 parts by mass / ethyl acetate 84 parts by mass The above was put into a vessel equipped with stirring blades, and the system was heated to 60 ° C. to dissolve stearyl stearate in ethyl acetate.
Next, the system was gradually cooled while gently stirring at 50 rpm, and cooled to 25 ° C. over 3 hours to obtain a milky white liquid.
This solution was put into a heat-resistant container together with 20 parts by mass of 1 mm glass beads and dispersed for 3 hours with a paint shaker to obtain a wax dispersion 1. When the wax particle size (dispersion size) in the wax dispersion 1 was measured with a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.), the number average particle size was 0.12 μm.

<Preparation of colorant dispersion>
Copper phthalocyanine pigment CI Pigment Blue 15: 3 8 parts by mass, pigment dispersant (manufactured by Ajinomoto Co .; Ajisper PB-822) 0.8 parts by mass, ethyl acetate 54 parts by mass In a heat-resistant glass container with 10 parts by mass of 1 mm glass beads The mixture was charged and dispersed for 5 hours in a paint shaker to obtain a colorant dispersion 1.

<Preparation of binder resin solution>
A polyester resin solution 1 was prepared by putting 140 parts by mass of ethyl acetate into a hermetically sealed container equipped with stirring blades and stirring the mixture at 100 rpm with the following resin powder and stirring at room temperature for 3 days.
(Resin powder)
Polyester resin using propylene glycol, ethylene glycol, butanediol, terephthalic acid and isophthalic acid as monomers (Mw6800, Mn2700, Mp5200, Tg = 50 ° C.)

<Preparation of liquid toner composition>
Wax dispersion 1 100 parts by weight Colorant dispersion 1 57 parts by weight Polyester resin solution 1 248 parts by weight

  The above solution was put into a container, and liquid toner composition 1 was prepared by stirring and dispersing at 1500 rpm for 10 minutes with a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).

<Preparation of aqueous phase>
The following was put into a container, and stirred at 5000 rpm for 1 minute with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
900 parts by mass of ion-exchanged water 28.8 parts by mass of resin fine particle dispersion 1
(4.5 parts by mass of resin fine particles are charged per 100 parts by mass of toner particles)
50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries)
0.04 parts by mass Ethyl acetate 40 parts by mass Next, the rotation of the TK homomixer was stopped, and the liquid toner composition 1 was added and allowed to stand for 30 minutes, so that the low molecular weight components of the binder resin were eluted in the aqueous phase. I let you.
<Emulsification and desolvation process>
Subsequently, the rotational speed of the TK homomixer was increased to 8000 rpm, and stirring was continued for 3 minutes to suspend the liquid toner composition.
Next, a stirring blade was set in the container, the system was heated to 50 ° C. while stirring at 200 rpm, and the solvent was removed over 5 hours in a state where the pressure was reduced to 500 mmHg to obtain an aqueous dispersion of toner particles. .

<Washing-drying process>
Next, the aqueous dispersion of toner particles was filtered and reslurried to 500 parts by mass of ion-exchanged water, and the system was stirred until hydrochloric acid was added to pH 4 and stirred for 5 minutes.
The slurry was filtered again, 200 parts by mass of ion exchange water was added, and the operation of stirring for 5 minutes was repeated three times to remove triethylamine remaining in the system, thereby obtaining a filter cake of toner particles.
Next, the above filter cake was dried with a hot air dryer at 45 ° C. for 3 days, and sieved with an opening of 75 μm mesh to obtain toner particles 1. Table 1-1 shows the formulation of the wax dispersion, and Table 1-2 shows the formulation of the toner particles.

<Measurement of frictional charge>
Using 6 parts by mass of the toner particles and 94 parts by mass of a magnetic ferrite carrier coated with a silicone resin and having a weight average particle size of 35 μm, the triboelectric charge was measured by the above-described method. It showed charging characteristics. Table 2-1 shows the triboelectric charge amounts of the toner particles of Examples and Comparative Examples of the present invention.

<Preparation of toner>
Next, with respect to 100 parts by mass of the toner particles 1, the hydrophobic silica having an average diameter of 20 nm is 0.7.
Toner 1 was obtained by mixing 0.8 part by mass of monodispersed silica having an average diameter of 120 nm with a Henschel mixer.

<Physical properties of toner>
Tables 2-1 and 2-2 show the physical properties of the toners of Examples and Comparative Examples.
When the dispersion state of the wax in the toner 1 was confirmed, it was acicular with a major axis of 2.07 μm, a minor axis of 0.14 μm, and a major axis / minor axis = 14.8. The dispersion shape of the wax was considered to be achieved by packing the wax dispersion grains in the toner in a needle shape because the short diameter is close to the wax dispersion diameter in the wax dispersion.

<Electrophotographic characteristics of toner>
Table 3 shows the electrophotographic characteristics of the toners of Examples and Comparative Examples.
Toner 1 was excellent in low-temperature fixability, and further excellent in heat storage stability and offset resistance.

<Example 2>
A wax dispersion 2 was prepared in the same manner as in Example 1 except that stearyl stearate was used as the wax in <Preparation of wax dispersion> instead of behenyl behenate (melting point: 70 ° C.). The particle diameter (dispersion diameter) of the wax particles in the obtained dispersion was measured in the same manner as in Example 1. As a result, it was 0.15 μm.
Next, toner particles 2 were prepared in the same manner as in Example 1 except that the wax dispersion 1 was changed to the wax dispersion 2 in <Preparation of liquid toner composition>.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 1, it was -23.1 μC / g.
And had good charging characteristics.
Toner 2 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 2 was confirmed, it was a needle shape having a major axis of 1.79 μm, a minor axis of 0.11 μm, and a major axis / minor axis = 16.3.

<Electrophotographic characteristics of toner>
Toner 2 was excellent in low-temperature fixability, and further excellent in heat-resistant storage stability and offset resistance.

<Example 3>
A wax dispersion 3 was prepared in the same manner except that stearyl stearate was used as the wax in <Preparation of Wax Dispersion> in Example 1 except that sorbitan monobehenate (melting point: 73 ° C.) was used. The particle diameter (dispersion diameter) of the wax particles in the obtained dispersion was measured in the same manner as in Example 1. As a result, it was 0.22 μm.
Next, toner particles 3 were prepared in the same manner except that the wax dispersion 1 was changed to the wax dispersion 3 in <Preparation of liquid toner composition> in Example 1.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 1, it was -25.4 μC / g.
And had good charging characteristics.
Toner 3 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 3 was confirmed, the major axis was 1.98 μm and the minor axis was 0.8.
The needle shape was 19 μm, major axis / minor axis = 10.4.

<Electrophotographic characteristics of toner>
Toner 3 was excellent in low-temperature fixability, and further excellent in heat-resistant storage stability and offset resistance.

<Example 4>
In Example 1 <Preparation of Wax Dispersion>, stearyl stearate was used as the wax. Carnauba wax (80 to 85% wax acid and alcohol ester, 1.
A wax dispersion 4 was prepared in the same manner except that it was changed to 5% to 3% hydrocarbons (from Celerica NODA, natural wax product guide). The particle diameter (dispersion diameter) of the wax particles in the obtained dispersion was measured in the same manner as in Example 1. As a result, it was 0.15 μm.
Next, toner particles 4 were prepared in the same manner as in Example 1 except that the wax dispersion 1 was changed to the wax dispersion 4 in <Preparation of liquid toner composition>.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 1, it was -26.8 μC / g.
And had good charging characteristics.
Toner 4 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 4 was confirmed, it was needle-shaped with a major axis of 2.01 μm, a minor axis of 0.15 μm, and a major axis / minor axis = 13.4.

<Electrophotographic characteristics of toner>
Toner 4 was excellent in low-temperature fixability, excellent in heat-resistant storage stability, in particular, no offset was observed at all, and extremely excellent in offset resistance. This was probably because carnauba wax contained a low-polarity hydrocarbon wax of 1.5% to 3% and thus exhibited a sufficient release effect without being compatible with the polyester resin.

<Example 5>
In Example 1, <Preparation of Wax Dispersion>, 16 parts by weight of stearyl stearate was used as the wax. ) A wax dispersion 5 was prepared in the same manner except that the amount was changed to 2 parts by mass. The particle diameter (dispersion diameter) of the wax particles in the obtained dispersion was measured in the same manner as in Example 1. As a result, it was 0.18 μm.
Next, toner particles 5 were prepared in the same manner except that the wax dispersion 1 was changed to the wax dispersion 5 in <Preparation of liquid toner composition> in Example 1.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 1, it was -24.8 μC / g.
And had good charging characteristics.
Toner 5 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 5 was confirmed, the major axis was 1.99 μm and the minor axis was 0.7.
The needle shape was 11 μm and major axis / minor axis = 18.1.

<Electrophotographic characteristics of toner>
Toner 5 was excellent in low-temperature fixability, excellent in heat-resistant storage stability, in particular, no offset was observed at all, and extremely excellent in offset resistance. This was thought to be because the release effect was fully expressed without being compatible with polyester because paraffin wax with extremely low polarity was used in combination with carnauba wax.

<Example 6>
A wax dispersion 6 was prepared in the same manner except that stearyl stearate was used as the wax in <Preparation of Wax Dispersion> in Example 1 except that it was changed to trimethylolpropane tribehenate (melting point: 58 ° C.). did. The particle diameter (dispersion diameter) of the wax particles in the obtained dispersion was measured in the same manner as in Example 1. As a result, it was 0.11 μm.
Next, toner particles 6 were prepared in the same manner as in Example 1 except that the wax dispersion 1 was changed to the wax dispersion 6 in <Preparation of liquid toner composition>.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 1, it was -25.8 μC / g.
And had good charging characteristics.
Toner 6 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 6 was confirmed, it was acicular with a major axis of 1.96 μm, a minor axis of 0.13 μm, and a major axis / minor axis of 15.1.

<Electrophotographic characteristics of toner>
In the toner 6, although the high temperature offset was observed to be slightly remarkable at a temperature lower than that in Example 1, it was not problematic.
This toner was inferior to Example 1 in offset resistance because of the bulky structure in which the alkyl moiety of the alcohol component of the wax used had a branched structure, and a fatty acid was bonded to each of the branched chains. Therefore, the mobility in the polyester matrix in the molten state is low, or it is difficult to ooze out from the highly polar surface layer of the present invention.

<Example 7>
A wax dispersion 7 was prepared in the same manner except that stearyl stearate was used as the wax in Example 1 <Preparation of wax dispersion> was changed to pentaesthritol monostearate (melting point: 52 ° C.). did. The particle diameter (dispersion diameter) of the wax particles in the obtained dispersion was measured in the same manner as in Example 1. As a result, it was 0.15 μm.
Next, toner particles 7 were prepared in the same manner except that the wax dispersion 1 was changed to the wax dispersion 7 in <Preparation of liquid toner composition> in Example 1.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 1, it was -26.1 μC / g.
And had good charging characteristics.
Toner 7 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 7 was confirmed, it was needle-shaped with a major axis of 2.04 μm, a minor axis of 0.17 μm, and a major axis / minor axis of 12.0.

<Electrophotographic characteristics of toner>
In the toner 7, although the high temperature offset is observed at a temperature lower than that in the first embodiment, the level is lighter than that in the sixth embodiment and is not problematic.
The toner 7 was inferior in offset property to that of Example 1 because the alkyl part of the alcohol component of the wax used had a branched structure, and the mobility in the polyester matrix in the molten state was low. It seems that it was difficult to exude from the highly polar surface layer of the invention. However, since only one fatty acid is bonded to the alcohol and the degree of the branched structure is smaller than that of Example 6, the degree of offset seems to be better than that of Example 6.

<Example 8>
A wax dispersion 8 was prepared in the same manner as in Example 1 except that stearyl stearate was used as the wax in <Preparation of wax dispersion> instead of stearic acid monoglyceride (melting point 65 ° C.). When the particle diameter (dispersion diameter) of the wax particles in the obtained dispersion was measured in the same manner as in Example 1, it was 0.16 μm.
Next, toner particles 8 were prepared in the same manner except that the wax dispersion 1 was changed to the wax dispersion 8 in <Preparation of liquid toner composition> in Example 1.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 1, it was -24.6 μC / g.
And had good charging characteristics.
Toner 8 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 8 was confirmed, it was needle-shaped with a major axis of 1.71 μm, a minor axis of 0.14 μm, and a major axis / minor axis of 12.2.

<Electrophotographic characteristics of toner>
In the toner 8, although the high temperature offset is observed at a temperature lower than that in the first embodiment, the level is lighter than that in the sixth embodiment and is not problematic.
The toner 8 was inferior in offset resistance to that of Example 1 because the alkyl moiety of the alcohol component of the wax used had a branched structure, so the mobility in the polyester matrix in the molten state was low, It seems that it was difficult to exude from the highly polar surface layer of the present invention. However, since only one fatty acid is bonded to the alcohol and the degree of the branched structure is smaller than that of Example 6, the degree of offset seems to be better than that of Example 6.

<Example 9>
In Example 4 <Preparation of Wax Dispersion>, 16 parts by weight of carnauba wax and 8 parts by weight of wax dispersant were used, but 24 parts by weight of carnauba wax and 4.8 parts by weight of wax dispersant were used. A wax dispersion 9 was prepared in the same manner except that the parts were changed to parts. The particle diameter (dispersion diameter) of the wax particles in the obtained dispersion was measured in the same manner as in Example 4. As a result, it was 0.47 μm, which was larger than the particles in the wax dispersion 4. This was presumably because the wax dispersion 9 had a higher wax concentration relative to the ethyl acetate and a lower wax dispersant concentration relative to the wax than the wax dispersion 4.

Next, toner particles 9 were prepared in the same manner except that the wax dispersion 4 was replaced with the wax dispersion 9 in <Preparation of liquid toner composition> in Example 4.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 4, it was -26.3 μC / g.
And had good charging characteristics.
Toner 9 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 9 was confirmed, the major axis was slightly large and the needle was slightly thick, with a major axis of 2.19 μm, a minor axis of 0.68 μm, and a major axis / minor axis = 3.2.
The short and long diameters were slightly larger and thick needles because the particle size of the wax particles in the wax dispersion was large and the wax particles were agglomerated due to the small amount of wax dispersant. It seemed to be good.

<Electrophotographic characteristics of toner>
Toner 9 was slightly inferior in heat-resistant storage as compared with Example 4, but was not problematic. This was probably because the wax was slightly larger on the toner surface during storage because the major axis of the wax was slightly larger. Moreover, although there was no problem, the offset resistance and the low-temperature fixability were slightly inferior. This was probably because the dispersion shape of the wax was slightly thick, so that the toner was not easily crushed and the wax was difficult to ooze out.

<Example 10>
A wax dispersion 10 was prepared in the same manner as in Example 4 <Preparation of wax dispersion> except that 8 parts by mass of the wax dispersant was used and that the wax dispersant was changed to 2 parts by mass. The particle diameter (dispersion diameter) of the wax particles in the obtained dispersion was measured in the same manner as in Example 4. As a result, the particle diameter was 0.48 μm, which was larger than the particle diameter of the particles in the wax dispersion 4. there were. This was presumably because the wax dispersion 10 was a dispersion having a lower concentration of the wax dispersant relative to the wax than the wax dispersion 4.

Next, toner particles 10 were prepared in the same manner except that the wax dispersion 4 was changed to the wax dispersion 10 in <Preparation of liquid toner composition> in Example 4.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 4, it was -24.8 μC / g.
And had good charging characteristics.
Toner 10 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 10 was confirmed, it was a thick needle having a major axis of 1.16 μm, a minor axis of 0.61 μm, and a major axis / minor axis of 1.9.
This is because the particle size of the wax particles in the wax dispersion was large in the first place, and because there were few wax dispersants, the wax particles aggregated more strongly in the toner, and the tendency to stack in a needle shape was weakened. There seemed to be.

<Electrophotographic characteristics of toner>
The toner 10 is of no problem as compared with Example 4, but was slightly inferior in both low-temperature fixability and offset resistance. This was thought to be because the toner was difficult to be crushed because the needle-like character was thin in the dispersed shape of the wax.

<Example 11>
In Example 4 <Preparation of Wax Dispersion>, 16 parts by weight of carnauba wax and 8 parts by weight of wax dispersant were used, but 8 parts by weight of carnauba wax and 12.8 parts by weight of wax dispersant were used. A wax dispersion 11 was prepared in the same manner except that the parts were changed to parts. The particle diameter (dispersion diameter) of the wax particles in the obtained dispersion was measured in the same manner as in Example 4. As a result, it was 0.05 μm, which was smaller than the particles in the wax dispersion 4. This was probably because the wax dispersion 11 had a high concentration of the wax dispersant relative to the wax.

Next, toner particles 11 were prepared in the same manner except that the wax dispersion 4 was changed to the wax dispersion 11 in <Preparation of liquid toner composition> in Example 4.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 4, it was -26.7 μC / g.
And had good charging characteristics.
Toner 11 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 11 was confirmed, it had a very thin needle-like structure with a major axis of 1.51 μm, a minor axis of 0.05 μm, and a major axis / minor axis of 30.2.
This was probably because the particle size of the wax particles in the wax dispersion liquid was small in the first place, and the aggregation of the wax particles in the toner was extremely suppressed due to the relatively large amount of the wax dispersant.

<Electrophotographic characteristics of toner>
Toner 11 was inferior in offset resistance to the extent that there was no problem compared to Example 4.
This is because the wax has a very thin needle-like structure, so the area in contact with the polyester resin is increased and the wax is easily compatible with the polyester resin, so the effect as a mold release agent is reduced. It was thought that it was because of.

<Example 12>
In <Preparation of Wax Dispersion> in Example 4, 16 parts by weight of carnauba wax and 8 parts by weight of wax dispersant were used, so that 8 parts by weight of carnauba wax and 10 parts by weight of wax dispersant were used. A wax dispersion 12 was prepared in the same manner except that it was changed. The particle diameter (dispersion diameter) of the wax particles in the obtained dispersion was measured in the same manner as in Example 4.
The particle diameter was 09 μm, which was smaller than the particles in the wax dispersion 4. This was probably because the wax dispersion 12 had a high concentration of the wax dispersant relative to the wax.
Next, toner particles 12 were prepared in the same manner except that the wax dispersion 4 was replaced with the wax dispersion 12 in <Preparation of liquid toner composition> in Example 4.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 4, it was -24.8 μC / g.
And had good charging characteristics.
A toner 12 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 12 was confirmed, it had a slightly thin needle-like structure with a major axis of 1.81 μm, a minor axis of 0.09 μm, and a major axis / minor axis = 20.1.
This was probably because the particle size of the wax dispersion liquid was small in the first place, and the aggregation of wax particles in the toner was extremely suppressed due to the relatively large amount of wax dispersant.

<Electrophotographic characteristics of toner>
The toner 12 was inferior to the offset resistance compared with Example 4 although there was no problem.
This is because, as in Example 11, the wax had a thin needle-like structure, so the area in contact with the polyester resin was increased, and it became easier to dissolve in the polyester resin, so that it was effective as a release agent. Seemed to be thinner.

<Example 13>
In <Preparation of Wax Dispersion> in Example 4, 16 parts by mass of carnauba wax and 8 parts by mass of wax dispersant were used, so that 8 parts by mass of carnauba wax and 4 parts by mass of wax dispersant were used. A wax dispersion 13 was prepared in the same manner except that it was changed. This dispersion 13 is obtained by reducing the amount of the wax and the wax dispersant without changing the ratio of the wax and the wax dispersant as compared with the wax dispersion 4.
The particle diameter (dispersion diameter) of the wax particles in the obtained dispersion was measured in the same manner as in Example 4. As a result, it was 0.12 μm.
Next, toner particles 12 were prepared in the same manner except that the wax dispersion 4 was changed to the wax dispersion 13 in <Preparation of liquid toner composition> in Example 4.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 4, it was -28.1 μC / g.
And had good charging characteristics.
A toner 13 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 13 was confirmed, it was needle-shaped with the major axis being 1.11 μm, the minor axis being 0.11 μm, and the major axis / minor axis = 10.1.

<Electrophotographic characteristics of toner>
The toner 13 was slightly inferior to the offset property as compared with Example 4, but had no problem. This was probably because the amount of wax was smaller than that in Example 4.

<Example 14>
In <Preparation of Wax Dispersion> in Example 4, carnauba wax was used in an amount of 16 parts by mass and a wax dispersant was used in an amount of 8 parts by mass, so that carnauba wax was 32 parts by mass and the wax dispersant was 16 parts by mass. A wax dispersion 14 was prepared in the same manner except that it was changed. The wax dispersion 14 is obtained by increasing the amount of the wax and the wax dispersant without changing the ratio of the wax and the wax dispersant as compared with the wax dispersion 4.
The particle diameter (dispersion diameter) of the wax particles in the obtained dispersion was measured in the same manner as in Example 4. As a result, it was 0.15 μm.
Next, toner particles 14 were prepared in the same manner except that the wax dispersion 4 was changed to the wax dispersion 14 in <Preparation of liquid toner composition> in Example 4.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 4, it was -27.6 μC / g.
And had good charging characteristics.
Toner 14 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 14 was confirmed, it was a slightly thick needle having a major axis of 1.84 μm, a minor axis of 0.34 μm, and a major axis / minor axis = 5.4. This was thought to be because the total amount of wax was large, so that the wax aggregates stacked in a needle shape were further stacked to increase the apparent short diameter.

<Electrophotographic characteristics of toner>
The toner 14 was slightly inferior in heat resistant storage stability as compared with Example 4. This was probably due to the large amount of wax.
Further, the toner 14 was slightly inferior in both the low-temperature fixability and the offset resistance as compared with Example 4. This seems to be because the toner was hard to be crushed because the dispersion state of the wax was a slightly thick needle shape.

<Example 15>
A wax dispersion 15 was prepared in the same manner as in Example 1 <Preparation of wax dispersion> except that 16 parts by mass of stearyl stearate was used as the wax in place of myristyl myristate (melting point: 40 ° C.). . The particle diameter (dispersion diameter) of the wax particles in the obtained dispersion was measured in the same manner as in Example 1. As a result, it was 0.12 μm.
Next, toner particles 15 were prepared in the same manner except that the wax dispersion 1 was changed to the wax dispersion 9 in <Preparation of liquid toner composition> in Example 1.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 1, it was -26.9 μC / g.
And had good charging characteristics.
A toner 15 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 15 was confirmed, it was needle-shaped with a major axis of 1.93 μm, a minor axis of 0.14 μm, and a major axis / minor axis = 13.8.

<Electrophotographic characteristics of toner>
Toner 15 was inferior in heat-resistant storage stability as compared with Example 1 although there was no problem. This was thought to be due to the low melting point of the wax.

<Example 16>
The same procedure as in Example 1 <Preparation of wax dispersion> except that 16 parts by weight of stearyl stearate was used as the wax was changed to a montanic acid derivative wax (Hoechst, Hoechst Wax FL, melting point 101 ° C.). Thus, a wax dispersion 16 was prepared. When the particle size of the wax particles in the obtained dispersion was measured in the same manner as in Example 1, it was 0.14 μm.
Subsequently, toner particles 16 were prepared in the same manner as in Example 1 except that the wax dispersion 1 was changed to the wax dispersion 16 in <Preparation of liquid toner composition>.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 1, it was -24.6 μC / g.
And had good charging characteristics.
Toner 16 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 16 was confirmed, it was acicular with a major axis of 1.91 μm, a minor axis of 0.13 μm, and a major axis / minor axis = 14.7.

<Electrophotographic characteristics of toner>
The toner 16 was inferior in both low-temperature fixability and offset resistance as compared with Example 1, but to the extent that there was no problem. This was thought to be due to the high melting point of the wax.

<Example 17>
In the <emulsification and desolvation step> of Example 1, 28.8 parts by mass of the resin fine particle dispersion 1 (
Except for the fact that 4.5 parts by mass of resin fine particles per 100 parts by mass of toner was used, 12.2 parts by mass (1.9 parts by mass of resin fine particles per 100 parts by mass of toner) was used. In the same manner, toner particles 17 were prepared.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 1, it was -24.8 μC.
/ G and good charging characteristics.
Toner 17 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 17 was confirmed, it was acicular with a major axis of 1.98 μm, a minor axis of 0.15 μm, and a major axis / minor axis of 13.2.

<Electrophotographic characteristics of toner>
Toner 17 was inferior in heat resistant storage compared to Example 1. This was thought to be due to the small amount of resin fine particles forming the surface layer.

<Example 18>
In the <emulsification and desolvation step> of Example 1, 28.8 parts by mass of the resin fine particle dispersion 1 (
The procedure was the same except that the resin fine particles (4.5 parts by mass charged with respect to 100 parts by mass of the toner) were changed to 96 parts by mass (100 parts by mass of toner with 15 parts by mass of the resin fine particles charged). Toner particles 18 were prepared.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 1, it was -24.8 μC.
/ G and good charging characteristics.
A toner 18 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 18 was confirmed, it was needle-shaped with a major axis of 1.80 μm, a minor axis of 0.15 μm, and a major axis / minor axis = 12.0.

<Electrophotographic characteristics of toner>
Toner 18 was inferior in low-temperature fixability and offset resistance as compared with Example 1. This was thought to be because there were many resin fine particles forming the surface layer, and it was difficult for heat to be transmitted and the wax was not easily oozed out.

<Example 19>
In Example 1 <Preparation of Wax Dispersion>, 16 parts by weight of stearyl stearate were used as the wax. Beeswax (melting point 65 ° C .: ester wax 66%, hydrocarbon 25%, Celerica NODA Corporation, natural A wax dispersion 17 was prepared in the same manner except that the wax product guide was changed. The particle diameter of the wax particles in the obtained dispersion was measured in the same manner as in Example 1. As a result, it was 0.18 μm.
Next, toner particles 19 were prepared in the same manner except that the wax dispersion 1 was changed to the wax dispersion 17 in <Preparation of liquid toner composition> in Example 1.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 1, it was -24.1 μC / g.
And had good charging characteristics.
A toner 19 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the toner 19 was confirmed, it was needle-shaped with a major axis of 1.72 μm, a minor axis of 0.22 μm, and a major axis / minor axis = 7.8.
<Electrophotographic characteristics of toner>
Toner 19 was inferior in offset resistance compared to Example 1. This was thought to be because it was difficult for the hydrocarbons with low polarity to ooze out to the surface because the proportion of hydrocarbons in beeswax was as high as 25%.

<Comparative Example 1>
In the same manner as in Example 1, a colorant dispersion 1 and a polyester resin solution 1 were prepared.
<Preparation of liquid toner composition>
Colorant dispersion 1 57 parts by weight Polyester resin solution 1 248 parts by weight Stearyl stearate (melting point 60 ° C) 14.8 parts by weight Nitrile group-containing styrene acrylic resin (styrene 65 parts by weight, n-butyl acrylate 35 parts by weight) Part, acrylonitrile 10 parts by mass, peak molecular weight 8500)

7.4 parts by mass / ethyl acetate 77.8 parts by mass The above substance was transferred to a closed vessel equipped with a stirring blade, the system was heated to 60 ° C. while stirring at 100 rpm, and stirred at the same temperature for 10 minutes. The wax was completely dissolved.
Subsequently, <Preparation of aqueous phase> in Example 1 was performed, and the emulsification step in <Emulsification and desolvation step> was performed in a state where the inside of the system was maintained at 60 ° C. Then, the desolvation step similar to Example 1 was performed. Then, the same operation as in <Washing to drying step> was performed to obtain comparative toner particles 1.
When the triboelectric charge amount of the comparative toner particles was measured in the same manner as in Example 1, it was -24.7 μC.
/ G and good charging characteristics.
Comparative toner 1 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the comparative toner 1 was confirmed, it was a substantially spherical shape having a major axis of 1.54 μm, a minor axis of 1.46 μm, and a major axis / minor axis of 1.1. The reason why this toner was not spherical in shape was probably because the wax dispersion was not prepared in advance and was introduced into the toner in a molten state, so that the wax aggregated when solidified.

<Electrophotographic characteristics of toner>
When the fixing test of Comparative Toner 1 was performed in the same manner as in Example 1, the toner showed offset and wrapping at temperatures lower than 180 ° C., and was clearly inferior in offset resistance. This was thought to be because the wax was not dispersed in a needle shape, so that the toner was difficult to crush and it was difficult for the wax to ooze out. In addition, although there was no problem, the low-temperature fixability was slightly inferior. This was also because the toner was not easily crushed because the wax was not needle-shaped.

<Comparative example 2>
<Preparation of wax dispersion>
A wax dispersion was prepared by the same formulation and method as in Example 1 as follows.
Stearyl stearate (melting point: 60 ° C.) 10 parts by mass Nitrile group-containing styrene acrylic resin (65 parts by mass of styrene, 35 parts by mass of n-butyl acrylate, 10 parts by mass of acrylonitrile, peak molecular weight 8500)

8 parts by mass / ethyl acetate 84 parts by mass The above was put into a vessel equipped with stirring blades, and the system was heated to 60 ° C. to dissolve stearyl stearate in ethyl acetate.
Next, the system was gradually cooled while gently stirring at 50 rpm, and cooled to 25 ° C. over 3 hours to obtain a milky white liquid.
This solution was put into a heat-resistant container together with 20 parts by mass of 1 mm glass beads and dispersed for 3 hours with a paint shaker.
Furthermore, with the glass beads inserted, 24 parts by mass of a polyester resin (peak molecular weight 9800) grafted with styrene (St) was added and sufficiently dissolved. Further, by dispersing for 30 minutes with a paint shaker, a wax dispersion 18 coated with styrene (St) graft polyester was obtained.
The particle diameter (dispersion diameter) of the wax particles in the obtained dispersion was measured in the same manner as in Example 1. As a result, it was 0.12 μm.

Subsequently, in <Preparation of Liquid Toner Composition> in Example 1, 100 parts by mass of wax dispersion 1 was used, except that the wax dispersion 18 was changed to 122 parts by mass. The same comparative toner 2 was prepared with the same amount of wax.
When the triboelectric charge amount of the comparative toner particles was measured in the same manner as in Example 1, it was -23.9 μC / g and had good charging characteristics.
Comparative toner 2 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the comparative toner 2 was confirmed, it was a substantially spherical shape having a major axis of 0.13 μm, a minor axis of 0.12 μm, and a major axis / minor axis of 1.1. The reason why the toner was dispersed in a spherical shape was that the wax surface was coated with polyester, so that the dispersibility of the wax particles was good even in the polyester and no aggregation occurred.

<Electrophotographic characteristics of toner>
The fixing test of Comparative Toner 2 was conducted in the same manner as in Example 1. As a result, the toner showed offset and wrapping at temperatures lower than 180 ° C. and clearly inferior offset resistance. This was thought to be because the wax was not dispersed in a needle shape, so that the toner was difficult to crush and it was difficult for the wax to ooze out. In addition, although there was no problem, the low-temperature fixability was slightly inferior. This was also because the toner was not easily crushed because the wax was not needle-shaped.

<Comparative Example 3>
In the preparation of the wax dispersion of Example 1, 16 parts by mass of stearyl stearate was used as the wax except that 10 parts by mass of paraffin wax (Toyo Petrolite, HNP-9, melting point 75 ° C.) was used. In the same manner, a wax dispersion 19 was obtained. When the particle diameter of the wax particles in the obtained dispersion was measured in the same manner as in Example 1, it was 0.24.
It was μm.
Next, comparative toner particles 3 were prepared in the same manner except that the wax dispersion 1 was changed to the wax dispersion 19 in <Preparation of liquid toner composition> in Example 1.
When the triboelectric charge amount of the toner particles was measured in the same manner as in Example 1, it was -22.7 μC / g.
And had good charging characteristics.
Comparative toner 3 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the comparative toner 3 was confirmed, it was a slightly thick needle shape having a major axis of 1.78 μm, a minor axis of 0.74 μm, and a major axis / minor axis = 2.4.

<Electrophotographic characteristics of toner>
When the fixing test of the comparative toner 3 was performed in the same manner as in Example 1, the toner showed offset and wrapping at temperatures lower than 180 ° C., and was clearly inferior in offset resistance. This was thought to be because it was difficult to ooze out through the highly polar surface layer of the present invention because only the very low polarity paraffin wax was used for the wax. Moreover, although there was no problem, the low-temperature fixability was slightly inferior. This was thought to be because the toner was not easily crushed because the wax was slightly thick.

<Comparative Example 4>
In the preparation of the resin fine particle dispersion 1 of Example 1, 94 parts by mass (0.7 mol) of dimethylolpropanoic acid and 8 parts by mass of sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate Instead of using both parts (0.03 mol), carboxylic acid was similarly used except that 16 parts by mass (0.24 mol) of propylene glycol was increased to 64.7 parts by mass (0.97 mol). A resin fine particle dispersion 2 having no group or sulfonic acid group in the side chain was prepared.
In Example 1, 28.8 parts by mass (toner 1) of resin fine particle dispersion 1 was prepared during the preparation of the aqueous phase.
The resin fine particle dispersion 2 was used for 36.7 parts by mass (preparing 4.5 parts by mass of resin fine particles to 100 parts by mass of toner). Comparative toner particles 4 were prepared in the same manner except that.
When the triboelectric charge amount of the obtained comparative toner particles 4 was measured, it was -5.7 μC / g, and the value was extremely low, and the toner was extremely inferior in chargeability.
Comparative toner 4 was prepared in the same manner as in Example 1, and physical properties and fixing were evaluated in the same manner.

<Physical properties of toner>
When the dispersion state of the wax in the comparative toner 4 was confirmed, it was needle-shaped with a major axis of 2.00 μm, a minor axis of 0.15 μm, and a major axis / minor axis = 13.3. The particle size distribution of this toner was broader than other toners. This seems to be because the resin fine particles used did not contain polar groups such as carboxylic acid groups and sulfonic acid groups, so that the dispersion stability was poor and the granulation property was poor.

<Electrophotographic characteristics of toner>
When the fixing test of the comparative toner 4 was performed in the same manner as in Example 1, the toner was inferior in low-temperature fixing property. The reason for this is not clear, but due to poor charging characteristics, there was a variation in the toner application on the unfixed image, and it was considered that the evaluation method of the present invention was not in a state where sufficient evaluation was possible.

FIG. 3 is a schematic view of a cross section of toner particles of the present invention. It is a figure of the calculation method of Tg in this invention. It is the schematic of the triboelectric charge amount measuring apparatus in this invention.

Explanation of symbols

(A) Toner particles of the present invention (b) Wax dispersed in the toner particles of the present invention (c) Long diameter of the wax in the toner particles of the present invention (d) Short diameter of the wax in the toner particles of the present invention

1. Suction machine (at least the part in contact with the measurement container 2 is an insulator)
2 ... Metal measuring container 3 ... 500 mesh screen 4 ... Metal lid 5 ... Vacuum gauge 6 ... Air flow control valve 7 ... Suction port 8 ... Capacitor 9 ... Electrometer

Claims (11)

At least toner base particles (A) containing a binder resin (a), a colorant and a wax, and a surface layer (B) containing a resin (b) on the surface of the toner base particles (A). A toner having capsule-type toner particles,
The binder resin (a) is a resin mainly composed of polyester,
The resin (b) is a reaction product of at least a diol component and a diisocyanate component, and has a carboxylic acid group, a sulfonic acid group, a carboxylic acid group salt or a sulfonic acid group salt in the side chain,
The toner comprises an ester wax as a main component and is dispersed in a needle shape in toner particles.   The toner according to claim 1, wherein the ester wax is an ester of a linear aliphatic acid and a linear aliphatic alcohol.   The toner according to claim 1, wherein the ester wax is a monoester.   The major axis of the wax dispersed in the needle shape is 2.10 μm or less, and the ratio of the major axis to the minor axis (major axis / minor axis) of the wax dispersed in the needle shape is 2.0 or more and 30. The toner according to claim 1, wherein the toner is 0.0 or less.   The toner according to claim 1, wherein a content of the wax in the toner is 5.0% by mass or more and 20.0% by mass or less.   The toner according to claim 1, wherein the wax has a melting point of 60 ° C. or more and 90 ° C. or less in the DSC measurement of the toner.   The toner according to any one of claims 1 to 6, wherein the surface layer (B) is formed of fine particles containing at least the resin (b).   A solution obtained by dissolving or dispersing at least the binder resin (a), the colorant, and the wax in an organic medium in an aqueous medium in which fine particles containing the resin (b) as a main component are dispersed. The toner according to claim 1, wherein the toner particles are obtained by dispersing the dispersion, removing the solvent from the obtained dispersion, and drying.   The content of the fine particles mainly composed of the resin (b) is 2.0 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the toner particles. The toner according to any one of the above.   The toner according to claim 1, wherein the resin (b) is urethane-modified polyester.   Dissolution obtained by dissolving or dispersing at least the binder resin (a), the colorant and the wax in an organic medium in an aqueous medium in which fine particles mainly composed of the resin (b) are dispersed. The method for producing a toner according to claim 1, further comprising a step of dispersing the product or the dispersion, removing the solvent from the obtained dispersion, and drying.

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